Adsorption As a Process for Produced Water Treatment: a Review

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Adsorption As a Process for Produced Water Treatment: a Review processes Review Adsorption as a Process for Produced Water Treatment: A Review Roghayeh Yousef 1, Hazim Qiblawey 1,* and Muftah H. El-Naas 2 1 Department of Chemical Engineering, Qatar University, Doha P.O. Box 2713, Qatar; [email protected] 2 Gas Processing Center, College of Engineering, Qatar University, Doha P.O. Box 2713, Qatar; [email protected] * Correspondence: [email protected] Received: 14 October 2020; Accepted: 30 November 2020; Published: 16 December 2020 Abstract: Produced water (PW) is a by-product of oil and gas operations, and its production is foreseen to increase in the upcoming years. Such an increase is justified by various entities through their projection of the expected increase in the demand of oil and gas. The treatment of produced water is a significantly growing challenge for the oil and gas industry that requires serious attention. The first part of this review will present the underlying issue of produced water and relevant practices. With adsorption being defined as the least expensive treatment method, the second part will introduce general adsorption principals. The third part will describe the recent applications of adsorption for the treatment of PW with more focus of categorizing the adsorbents as natural and non-natural adsorbents. The main aim of this review is to shed light on the recent research related to PW treatment using adsorption. This is performed to highlight the shortcomings in PW adsorption research and recommend research pathways that can help in developing the field further. Keywords: adsorption; produced water; water treatment; oil water; separation 1. Introduction Large amounts of wastewater are generated during the oil and gas operations, and they are often referred to as produced water (PW). It is basically a combination of the water originally exiting in the wells, which is the formation water, and any additional water injected for enhanced oil and gas recovery. By far, this water is the largest produced volume by industry and can accommodate different contaminants, such as oil compounds, dissolved minerals, chemical compounds and dissolved solids [1–4]. The contaminants constituting PW can vary drastically depending on the geolocation and the petroleum product obtained [5]. To showcase this variation, Table1 shows a sample of PW concentrations and how they vary depending on the country. Based on this variation, it is difficult to assign generic characteristics to PW and its contaminants. Table 1. Examples of PW concentrations. PW Source Hydrocarbon Concentration (mg/L) Reference Yangtze Petrochemical Company (China) 6000 [4,6] Oil India Limited (India) 366 [4,7] Brazilian Oil Production (Brazil) 250 [8,9] BP AG Refinery (Germany) 200–1000 [8,10] Processes 2020, 8, 1657; doi:10.3390/pr8121657 www.mdpi.com/journal/processes Processes 2020, 8, 1657 2 of 22 PW contaminants could have detrimental effects on the aquatic environment, as this contaminated water is often discharged to surface water, especially for offshore operations. Depending on the geolocation of the discharge, a specific regulatory limit stands for the amount of contaminant present in PW [11,12]. Thus far, most countries in Europe, North/South America and the Middle East adopted near zero discharge regulations [13–17]. These regulations vary and in Table2, it is shown how PW discharge regulations differ depending on the country of operation. Table 2. Hydrocarbon discharge regulations in different countries. Country Hydrocarbon Discharge Regulatory Level (mg/L) Reference U.S.A 42 [15,16] Australia 30 [15,17] Colombia 15 Argentina 5 Discharge level is a topic of importance in the oil and gas industry due to the projected increase in demand for energy [18]. According to the IEA, the need for fossil fuel is expected to grow drastically in the upcoming years [19]. As a result, it is foreseen that the amount of PW from the oil and gas industry will increase [18]. The expected increase of PW is mainly related to two factors: (i) increased production of oil/gas and (ii) age of the oil/gas field. With these two factors, the increase of PW is projected to be more than the current levels [1,12,18]. Based on this expected increase, a treatment method that can handle large volumes of PW is required and this is while economically covering a range of contaminants. With these requirements and based on the literature available, the adsorption approach is the best treatment option that can deliver these requirements for PW. Adsorption treatment approach is reported to operate at low concentrations with less operation time and much lower cost than other treatment methods [20,21]. Lowering the cost of treatment gives potential to PW for reuse in several practices. Such practices can range from injection into petroleum wells to industrial and domestic usages [16]. Managing PW by reusing it gives an incentive to industries, as treatment assigns a value to PW in the economy [5]. While most previous adsorption review papers consider generalized point of views related to the adsorption process, this review focuses on the application of adsorption for produced water treatment. The aim is to evaluate the current output of PW adsorption research and present the potential of recent adsorption system studies. It is important to note that the inclusion of heavy metals in this review is based on the point view that heavy metals are potential contaminants in PW. Depending on the geolocation of PW, these metals can vary between barium, lead, copper, cadmium, chromium, iron, arsenic, mercury and zinc [22–25]. With an emphasis on these heavy metals being part of PW, this review paper will discuss adsorbent systems that target heavy metals and hydrocarbons. The first part of this review will explain the main principles of adsorption and how it is reported in the literature. The second part will focus on the adsorbents investigated with respect to PW and their main reported results. Finally, research recommendations from the authors’ point-of-view are stated for the guidance on how the field of PW adsorption should evolve. 2. Adsorption In the literature, the materials used for PW are commonly assessed by characterization, kinetics and isotherms [26]. On a molecular level, adsorption is a process where attractive forces associate a solute (adsorbate) to a solid surface (adsorbent). The solid material used for the adsorption consists of a porous medium with a high internal surface area [27]. It is a common practice in the literature to describe these solid media by the parameters shown in Figure1. Processes 2020, 8, 1657 3 of 22 Figure 1. Common parameters for describing adsorption systems in the literature. 2.1. Characterization To gain a microscopic insight into how adsorption of PW contaminant occurs, characterizing the adsorbent system is often necessary. A solid with a good adsorption capacity should exhibit explicit characteristics that are related to the adsorbent’s surface area and internal network of pores [27]. According to IUPAC, an adsorbent can satisfy these characteristics by having a pore size between 2 nm to 50 nm [28]. 2.2. Kinetics Through the PW related literature, various studies have reported the kinetics of the adsorption system through conducting time interval experiments. These experiments are based on withdrawing a sample at specified time intervals and measuring the concentration [29]. The obtained data are used to build a profile and fit a suitable kinetics model that can describe the adsorption system. Based on the model, the adsorption mechanism can be identified [30]. From the many different kinetics models, the most common models in PW adsorption were observed to be: pseudo-first order, pseudo-second order, intraparticle diffusion model [31]. In terms of the pseudo-first order, if this model is confirmed by the experimental data, adsorption is taking place through physical forces [32]. With regards to pseudo-second order, using this model to fit the experimental data well, declares that adsorption mechanism is occurring through chemical means [33]. To further explore the chemical means, Elovich model is suggested as a kinetic model in the PW literature. This model accounts for predicting the mass and surface diffusion along activation energies [34]. Proportionate to the pseudo orders and Elovich model, the intraparticle diffusion model is a kinetics model with multiple mentions in the literature. This model is an indication that the intraparticle diffusion is the rate limiting step for adsorption. This is with the experimental data fitting the model and passing through the origin [35,36]. Table3 contains a summary of these models with their mathematical expressions. It is worth noting that most adsorption studies related to PW in this work reported kinetics being very well described by pseudo-second order model as illustrated in the following references: [37–39]. To state this decisively, studies compared the fit of pseudo-first/second order, Elovich or intraparticle diffusion models when applicable as shown in these examples: [40–43]. Table 3. Common kinetics models in PW. Model Name Equation Mechanism dqt Pseudo—first order dt = k1(qe − qt) [44] Physical adsorption dqt 2 Pseudo—second order dt = k2(qe − qt) [45] Chemisorption dqt −bqt Elovich dt = aexp [34] Chemisorption 1 Intraparticle diffusion qt = kit 2 [36,46] Intramolecular diffusion Processes 2020, 8, 1657 4 of 22 Where qe is the equilibrium adsorbate adsorbed in (mg/g), qt is the amount of adsorbate at time t and k is the equilibrium rate constant of the model. a in the Elovich model is the initial rate of adsorbent and b is the relationship to surface coverage extent and chemisorption activation energy. 2.3. Isotherms The most frequent assessment observed in the investigations of adsorption systems is fitting the adsorption equilibrium data in terms of isotherm models. The equilibrium relationship between the adsorbent and the adsorbate are explained in the literature through various expressions.
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